PII: S0043-1354(00)00044-0

Wat. Res. Vol. 34, No. 11, pp. 29712978, 2000

7 2000 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0043-1354/00/$ - see front matter

www.elsevier.com/locate/watres

MERCURY REMOVAL FROM WATER BY ION

EXCHANGE RESINS ADSORPTION
S. CHIARLE, M. RATTO* and M. ROVATTI
Dipartimento di Ingegneria Ambientale, Universita di Genova, via Opera Pia 15, 16145 Genova, Italy
(First received 1 October 1998; accepted 1 August 1999)
AbstractIn this paper a detailed experimental and theoretical analysis of the adsorption process of
mercury by ion exchange resins is presented. Experiments have been performed to study adsorption
eciency, the eect of pH on the uptake of mercury and the adsorption kinetics. The experimental
apparatus was a batch mechanically stirred reactor (volume 1.5 dm3), under almost isothermal
conditions (20.18C). The resin used in this study is Duolite GT-73, a chelating resin, macroreticular
with thiol (S-H) functional groups. The studied resin has a very high adsorption eciency, reaching
3040% in weight and the eciency decreases, decreasing pH, due to competition between ions H+
and Hg2+. Such a high eciency conrms previous results and justies the great interest for the
application of ion exchange resins in water treatment plants. As in previous works, measurements of
process kinetics show that the adsorption rate decreases as the initial mercury concentration is
increased. This fact suggests that intraparticle diusion rate can be the controlling step for the
adsorption process. To verify this, a simplied mathematical model has been identied, accounting for
a diusional resistance inside solid particles and where the equilibrium relationship between Hg
concentration in the liquid and in the solid is described by the Freundlich isotherm, neglecting H+
competition: this model is very eective in the prediction of the change in the adsorption kinetics with
the initial Hg concentration. Hence this preliminary approach can be held as the reference starting
point for the adsorption model: further developments will concern the equilibrium thermodynamics
(H+ competition). 7 2000 Elsevier Science Ltd. All rights reserved
Key wordsmercury adsorption, ion exchange resins, adsorption kinetics, diusional model, adsorption
model

NOMENCLATURE

b
c
DM
De
kF
kL
nF
mres
q
qMAX
qqs
R

second coecient in the Langmuir isotherm

Hg concentration in the liquid, mg l1
molecular diusivity of Hg in water, cm2 s1
eective diusivity, cm2 s1
rst coecient in the Freundlich isotherm
rst coecient in the Langmuir isotherm, (mg
Hg) (g resin)1
second coecient in the Freundlich isotherm
mass of resin per litre of solution, g l1
Hg concentration in the solid, (mg Hg) (g resin)1
Hg solid concentration in equilibrium with the initial liquid concentration, (mg Hg) (g resin)1
average concentration of Hg in the solid particle,
(mg Hg) (g resin)1
asymptotic value of q in the Langmuir isotherm,
(mg Hg) (g resin)1
particle radius, cm

V
x
y
z
e
r
t

particle volume, cm3

dimensionless Hg concentration in the solid
dened as q/qMAX
dimensionless Hg concentration in the liquid
dened as c/c ext
0
dimensionless spatial co-ordinate dened as r/R
particle voidage
density of the resin, g l1
pore tortuosity

Subscripts
0
initial

equilibrium
Superscripts
ext
external

INTRODUCTION

Sh Sherwood number
t
time, s
tc
characteristic time for equilibrium
T
temperature, 8C

*Author to whom all correspondence should be addressed.

Tel.: +39-10-3532589; fax: +39-10-3532586; e-mail:
ratto@diam.unige.it

Many authors, in the past, studied the best method,

both from the economical and technological point
of view, to remove mercury and heavy metals in
general from supercial waters, with the aim of the
preservation of the entire ecosystem from the
damages due to their accumulation (see e.g. Humenick and Schoor, 1974; Logsdon and Symons, 1975;

2971

2972

S. Chiarle et al.

Knocke and Hemphill, 1981; Deshkar et al., 1990;

Barkley, 1991; Ritter and Bibler, 1992; Mazidji et
al., 1992; Zouboulis et al., 1993; Couillard and
Mercier, 1994; Pazirandeh et al., 1998).
Mercury is commonly transferred from water by
the following methods:
.
.
.
.

conventional coagulation;
chemical precipitation;
adsorption (both chemical and physical);
reverse osmosis.

Adsorption processes have been and actually are

the most applied in the industries, and consequently
the most studied. Logsdon and Symons (1975) studied the removal of mercury during the conventional water treatments, showing that mercury is
adsorbed on clay particles during coagulation.
Humenick and Schoor (1974) analysed the mercury
removal from water through chemical and physical
adsorption on activated carbons, obtaining good
results. Zouboulis et al. (1993) studied removal of
toxic metal ions from solutions using industrial
solid by-products. Deshkar et al. (1990) used bark
as the adsorbing material, observing good adsorption capacity with respect to mercury, also considering its low cost.
All the above mentioned materials present good
adsorption capacity, but in general they are not
able to reduce mercury concentration below discharge limits established in environment legislation.
Discharge limits are, e.g. 10 ppb in USA (Ritter
and Bibler, 1992), 5 ppb (Italian legislation),
whereas for drinking water the limit is 1 ppb for
the Italian legislation.
Such discharge requirements can be matched
using specic ion exchange resins, characterised by
a very high selectivity with respect to mercury: see
e.g. Ritter and Bibler (1992), Mazidji et al. (1992).
In particular, Ritter and Bibler (1992) studied the
performance of Duolite GT-73 ion exchange resin
in a large-scale process, discussing some operational
problems encountered and their remedy. This work
aims to perform an experimental and theoretical
study of the removal of mercury from water by ion
applying the same exchange resin as Ritter and
Bibler (1992) process and to evaluate:

(e.g. see Ritter and Bibler, 1992). Before each experiment,

the resin was dried by air, weighted and wetted by adding
distilled, deionised
water as described in the manual pro2
vided by Duolite supplier. Since the resin was already in
the desired ionic form (H+) the only conditioning needed
was a brief rinse to remove any leached material.
Stock mercury solutions were prepared from analytical
reagent grade mercury chloride.
Measurements of mercury concentration were performed
using a mercury analyser (MAS 5000, Perkin Elmer Corporation), employing the MAH-10.
Two kinds of experimental measurements have been carried out:
. batch sorption tests, to determine the adsorption eciency and the eect of pH on the mercury uptake;
. tests to study the adsorption kinetics.
Batch sorption tests were performed at 2020:1 ^ C; the
reaction mixture consisted of a total volume 0.5 l of solution containing 0.250 g of resin; mercury initial concentrations varied from 10 to 280 mg/l at dierent pH (2, 4
and 7). The desired level of initial pH was set by adding a
sucient quantity of HCl (solution 0.1 N). The reaction
mixture was mechanically agitated (impeller speed 100
rpm). At the end of the contact time (24 h for all measurements), the bottle reactor is removed from the mixer and
the supernatant analysed for mercury. Deionised water
was used to prepare mercury solutions.
Batch kinetic tests were conducted in the same reactor
of the batch sorption tests. The reaction mixture consisted
of a total volume 1 l of solution containing 0.50 g of
resin; initial mercury concentrations analysed were about
1, 10 and 100 mg/l. At xed time intervals a sample of solution was withdrawn and analysed. The impeller speed
was again 100 rpm. Deionised water was used to prepare
mercury solutions.
Adsorption eciency and eect of pH on mercury uptake
The equilibrium experimental data of the adsorption of
Hg onto the ion exchange resin are presented in Fig. 1.
Such data have been obtained after a contact time of 24 h
and at dierent initial pH values pH 2, 4, 7). The duration of 24 h was not an arbitrary choice of ours, but is
due to the fact that a tendency to an asymptotic behaviour
is observed only after such a long period.
It can be observed from this Figure that the lower the
initial pH, the lower the mercury uptake becomes. This
means that, in the investigated domain, the adsorption eciency reaches its maximum when the initial pH is 7. Furthermore, it was observed that the nal pH of the solution
decreased to values around 4, when the initial pH was 7,
and to values around 3.5, when the initial pH was 4. In

. adsorption eciency;
. eect of pH on the uptake of mercury;
. adsorption kinetics.
Furthermore a suitable mathematical model is
identied, able to describe the main phenomena
observed.
EXPERIMENTAL

All experimental analysis has been carried out in a

batch mechanically stirred reactor (volume
1.5 dm3). The
2
resin used in this study was Duolite GT-73, a polystyrene/divinylbenzene resin with thiol (S-H) functional
groups, which has been already studied by other authors

Fig. 1. Equilibrium data obtained with initial pH 2, 4, 7.

Mercury removal from water

more detail, in each set of experiments at constant initial
pH (4 or 7) the nal pH depended on the initial Hg2+
concentration c0: the higher the c0, the smaller the nal
pH. On the contrary, pH remained constant when the initial pH was 2. This can be explained in terms of the cation exchange between Hg2+ and H+:
. pH remains constant at pH 2 (excess of protons);
. the uptake is low when pH is low (competition).
Final pH values are also consistent with a global balance
of positive charges. In fact an initial concentration of
Hg2+ of 100 mg/l corresponds to about 5  104 mol/l
(molecular weight of Hg is 200.59 g/mol). With an adsorption eciency of 100%, we would have a nal concentration of H+ equal to 1  103 mol/l, i.e. pH 3:
Furthermore, the initial Hg concentration for equilibrium
measurements was always below the solubility limit (which
is about 60 ppmmg/l in air-free water, but increases by
a factor of 700 in the more typical case of an aqueous solution with dissolved air, Aylett, (1973) and no precipitation was observed, implying that the only removal
mechanism is adsorption-ion exchange.
The observed facts imply that a rigorous description of
equilibrium must consider a reaction scheme such as (Ritter and Bibler, 1992):
2R SH Hg 2 4 R S Hg S R 2H

2R SH Hg22 4 R S Hg Hg S R 2H 2
and, e.g. a binary adsorption equilibrium isotherm (Lopez
et al., 1992), accounting for competition between Hg2+
and H+ cations.
However, the main goal of this work is to verify if a
kinetic model, in which intraparticle diusion is the controlling step, is eective to describe the change of adsorption kinetics with the initial Hg concentration. Hence, as a
rst step, a simplied approach was applied, which considers a global equilibrium model neglecting competition
between Hg2+ and H+ cations. This allows, obviously,
only a partial description of the system; nonetheless, kinetic model results presented below are very eective in
describing adsorption kinetics for a given initial pH (variation with initial pH cannot be predicted). In particular,
for the analysis of adsorption kinetics, we considered the
case of initial pH 7:
The most used method of representing adsorption data
as a function of the adsorbed species only is to apply
adsorption isotherms. There are many forms of adsorption
isotherms and the most commonly used are the Langmuir
and Freundlich models:
q qs

b
c
1b
c

q kF
cnF

Experimental data of Fig. 1 were tted by both Langmuir

and Freundlich equations: both models t the experimental trends (tting parameters are shown in Table 1). How-

2973

ever, if we observe Fig. 1, a plateau is evident for the

three data series at dierent initial pH, corresponding to
the resin saturation, and only the Langmuir model is able
to account qualitatively for this eect. Nonetheless, since
both the Langmuir and the Freundlich model neglect proton competition which is a fundamental phenomenon of
ion exchange mechanisms, they are inadequate for a true
thermodynamic description: hence both models are simply
semi-empirical correlations. On the other hand, when
implementing the simplied adsorption kinetics model
(which is discussed in detail in The Model section), it was
observed that the experimental behaviour of the adsorption kinetics was best described by applying the Freundlich model. This means that the Freundlich curve better
describes the behaviour of the system at low mercury concentrations in the liquid (i.e. in the left part of Fig. 1, far
from saturation) and therefore it is more suitable for the
analysis of kinetics. As a consequence of this, we decided
to apply the Freundlich isotherm in the kinetic model, on
an empirical basis only, since it allows a best t of the experimental data of adsorption kinetics.
It seems interesting to evaluate the adsorption eciency
for low initial concentrations of Hg, on the basis of the
adsorption isotherm determined above. An interesting
example is the case of water with a high initial content of
Hg discharged by a rst treatment by chemical precipitation (e.g. by Na2S). The Hg concentration in the euent
of such a preliminary treatment can be, in the best cases,
50 ppb (i.e. 0.05 mg/l). If we compute the asymptotic
value of c for an initial concentration cext
0 0:05 mg/l (the
initial adsorbed quantity q0 is set to zero), by solving the
following easy system of equations (global mass balance
and equilibrium constraint) for mres 0:5 g/l:
c1 mres q1 cext
0
q1 kF C n1F

we obtain, with initial pH 7, c1 14  10 15 mg/l and

q1 10:1 mg/g. This means that the eciency of this resin
is very high even for very low initial concentration of Hg
(computed eciency is almost 100%). On the other hand,
since we observed that equilibrium time is high, such a
high level of purication can be attained only after a very
long period of time.
In conclusion it seems useful to underline that the following facts:
. adsorption eciency is very high also at very low Hg
concentration in the liquid and the measured adsorption
capacity of this resin is very high, reaching the 3040%
in weight at initial pH 7: similar results were obtained
in previous works and clearly explain the great interest
for the application of ion exchange resins to the treatment of water containing small heavy metals concentrations, but exceeding discharge limits (Ritter and
Bibler, 1992; Mazidji et al., 1992);
. the duration of the equilibrium measurements is very
long (24 h): the extremely high period of activity of this
resin is a very interesting property of this material and
will be discussed in the next sections.

Table 1. Fitting parameters for the Freundlich and Langmuir isotherms

Initial pH

Freundlich isotherm tting parameters

Langmuir isotherm tting parameters

7
4
2

kf =150.58
kf =126.51
kf =106.31

qs=358.7
qs=362.75
qs=215.75

nf =0.220
nf =0.283
nf =0.235

b = 0.466
b = 0.319
b = 1.43

2974

S. Chiarle et al.
adsorption kinetics is very high (the trend is almost vertical) for all values of the initial concentration and that it
rapidly decreases with time, above all for high initial Hg
concentrations. Since the initial kinetics is mainly related
to the external mass transfer resistance, this means that
the external diusion is very rapid and we can state, also
considering swirl-speed tests, that the external transfer is
not the rate limitation of the metal removal.
Furthermore, to identify the limiting kinetic step,
among reaction rate and intraparticle diusion, it is important to note that, in Fig. 3, the adsorption rate
changes, by changing the initial concentration and tend to
increase as the initial amount of Hg2+ ions decreases.
This suggests that the limiting step of adsorption kinetics
is represented by transport phenomena inside solid particles. In order to obtain a clearer comprehension and
description of these facts, a mathematical model has been
developed. This is described in the next section.

Fig. 2. Swirl-speed test: change in impeller speed at t =

28 min.
THE MODEL

Kinetics
In ion exchange systems, the following phenomena are
involved, relevant for the process kinetics:
. liquid lm diusion;
. diusion within the particle;
. rate of reaction.
In many practical cases, mass transfer is controlled by a
combination of resistances and consequently each step
needs to be considered.
For kinetic tests, mercury solutions in deionised water
at initial pH 7 were employed.
We distinguished between particle and lm diusion
control using swirl-speed tests: the speed of the rotary shaker was varied over run rate; a slope change of mercury
concentration vs. time curve, at dierent speeds, would indicate that the external liquid lm is controlling the
adsorption process. On the contrary, for particle diusion
or chemical rate control, no change in slope should be
observed.
Figure 2 shows swirl-speed tests carried out at c0 11
mg/l: no evident change in slope was observed in the sorption rate, implying that the eect of external diusion is
negligible in the range of times investigated.
In Fig. 3 the behaviour of the dimensionless concentration vs. time at dierent initial concentrations is, presented.
From the reported data it can be seen that the initial

Fig. 3. Batch sorption kinetic measurements: non-dimensional concentrations vs. time.

As in previous works (Deshkar et al., 1990;

Orhan and Buyukgungor, 1993; Ho et al., 1995), experiments show, that sorption kinetics changes with
the initial mercury concentration in the liquid. In
such previous studies, the mathematical description
of the system was addressed to the identication of
a rst order reaction rate constant, in order to t
the experimental data of the removal extent vs time.
This kind of description was justied by the chelating properties of such resins, by the small dimensions of the solid particles and by the hypothesis
that no diusion is present inside particles, but
reaction takes place at the external surface. With
this approach a very simple and quick description
of the system is obtained (mass transfer inside the
particles is not considered and no integration of
partial dierential equations is necessary). Nevertheless, since sorption kinetics changes with the initial concentration, such kinetic constants must be
adjusted in order to account for this aspect. Therefore it was necessary to introduce semi-empirical relationships for the constant vs. the initial
concentration (Ho et al., 1995). On the other hand,
as is usually observed in all adsorption processes
where adsorbate diuses inside particles, this fact
impies that some diusion phenomena must take
place inside particles, which limits the overall rate
of mercury sorption, and which justies the
observed change in sorption kinetics with the initial
mercury concentration.
One of the main goals of this study was therefore
to apply a model which can predict sorption kinetics for any value of the initial concentration.
The model consists of a local diusional model
inside the solid particles, which describes the mercury transfer from the liquid phase to the solid,
combined with a global mass balance, which allows
to determine the mercury concentration in the
liquid at each integration step.
The local model includes the following hypotheses:

Mercury removal from water

1. the system is isotherm;

2. chemical kinetics is not the rate limitation of the
mercury removal: the chemical reaction is therefore assumed instantaneous;
3. as a consequence of item 2, local equilibrium
between the Hg concentration in the liquid phase
and in the solid phase is supposed;
4. cation competition is neglected and no eect of
pH is considered: adsorption data are therefore
represented as a function of the adsorbed specie
only;
5. the equilibrium relationship is given by the
Freundlich isotherm (the motivations for this
choice are given in the previous section);
6. the adsorbent particles are spherical bodies, their
dimension and porosity are uniform;
7. the external diusion resistance has been
accounted for since, as described below, this has
some non-negligible eect at the very beginning
of the process;
8. the mass accumulation of the adsorbed component in the liquid phase in the pores of the
sorbent is negligible.
Subject to these assumptions the dynamic behaviour
of the system is described by the following
equations:
The diusion equation inside the solid particles


@c
1 @
@c
@q
Deff 2
r2
r
@t
r @r
@r
@t

which, neglecting as usual Hg accumulation in the

liquid phase (hypothesis 8), becomes:
r



@q
1 @
@c
Deff 2
r2
@t
r @r
@r

and global balance in the liquid phase (following hypothesis 6)

dcext
dq
mres
dt
dt

where
q

1
V

q dV

The local equilibrium constraint for the diusional

model inside the particles is given by the Freundlich
relationship:
q kF cnF

10

Equation (7) becomes, in dimensionless form,



@x
Deff
cext
1 @
2 @y
0

z


@t
@z
r
qmax R 2 z 2 @ z
with the boundary condition

11


@ y 
DM
Sh
yext ys
@ z z1
2Deff

2975

12

A similar model has been already applied by

Navarro et al. (1996), with some simplifying
assumptions: external resistance was neglected and
the Langmuir isotherm was linearised since they
operated at very low Hg concentration.
Model implementation
The model has been implemented under the same
operating conditions of with the experimental data
shown in Fig. 3 (previous section):
1
cext

0 1:2; 9:6; 114 mg l

V1 l

Particle size distribution: R 0:15  0:6 mm

mres 10:5 g=l
Initial pH 7

r11125 g=l

Impeller speed: 100 rpm

T 208C:

It can be seen that, in order to make a severe test

for the model, the initial Hg2+ concentration, c ext
0
has been varied for a very wide range (three orders
of magnitude).
To integrate the equations of the model, transport parameters have to be evaluated: DM, De and
Sh. Furthermore, since the particle size distribution
is quite wide, in Eq. (11) we have also an uncertainty about the ``eective'' value of R. To reduce
the degrees of freedom we assumed that all the
uncertainty is concentrated in De and set R 0:4
mm.
Parameter DM has been evaluated by applying
the equation of Wilke and Chang (Bird et al.,
1960), giving a value:
DM 3:15
10 5 cm s 1 :
As far as the external resistance is concerned, by
applying any of the relationships available in literature of the type:
Sh A BRea Scb :
a value Sh  1 is always obtained. This is in accordance with the experimental results of Figs 2
and 3, showing that external mass transfer resistance is negligible. Hence, in this work we applied a
value Sh 20, which is equivalent to a negligible
external mass transfer resistance.
The suitable value of De, on the other hand, can
be tted from experimental data. After a rst estimate, performed applying the formula:
E
Deff DM
t

with

E
0:1
t

2976

S. Chiarle et al.

the eective diusivity was slightly tuned in order

to best t the experimental data, by using a tting
value e=t 0:28:
Hence all the parameters of the model were evaluated a priori and the only tting parameter was
the ratio e/t.
The numerical integration of the model was performed by applying the control volume method,
with control of the error at each time step (relative
error 0.1%). The particle has been divided into a
120 elements grid of equal volume, to better follow
the steep concentration gradients which take place
at the beginning of adsorption. At each integration
step, the average concentration of mercury in the
solid (q- ) is computed and the concentration in the
liquid phase is calculated by applying the following
global balance, which is the analogue of Eq. (6):

cext cext
0 mres q

13

Model results
Results of the numerical computations, performed by always keeping the model parameters
constant and varying exclusively the initial Hg concentration are shown in Fig. 4.
The present model can satisfactorily predict batch
sorption kinetics. The decrease in the kinetics as the
initial concentration in increase can be explained in
terms of the coupled eect of diusion inside the
particles and high non-linearity of equilibrium relationship. In fact, applying a pure diusional
model or equivalently a diusional model with a
linear isotherm, no variation in the kinetics would
be observed, as well. Hence the model applied is
eective: this means that to neglect reaction rate in
the kinetics is a good assumption. On the other
hand, reaction (i.e. proton competition) cannot be
neglected in the equilibrium relationship: this will
be the object of future research.
Furthermore, we observed that adsorption lasts
for a very long period before attaining saturation,

Fig. 4. Sorption kinetics: comparison between experimental data and model predictions.

Table 2. Asymptotic values of the adsorption model

c ext
0 (mg/l)

t1 (h)

c1 (mg/l)

q1 (mg/g resin)

114
9.6
1.2

1 103
1 107
1 1010

5.13
8.6  105
6.8  109

215.7
19.2
2.4

with extremely low values of the residual Hg concentration in water (saturation times and residual
Hg are presented in Table 2).
In Table 2, the values of c1 and q1 have been
calculated by applying Eq. (5), while the characteristic time tc has been evaluated by applying the following equation:

tc

Deff
r
H
R2

 1

14

where, case by case,

H

q1
c1

This means that, even if after a few hours the

adsorption kinetics becomes very slow, the adsorption capability remains very high, with the possibility to obtain, at least in principle, an extremely
puried water: the problem, obviously, is the very
high residence time.
It is also interesting to note the eect of the
external resistance to mass transfer. From the
analysis of Fig. 5, the approximation Sh 4 1, or in
other words cs cest , is correct only for high initial
concentrations. The error of that approximation
becomes higher as c ext
is decreased, at the begin0
ning of the process. Again this is due to the high
non-linearity of the equilibrium relationship: in
terms of Sherwood number Sh 20, the external
resistance seem to be negligible; nevertheless, at the
beginning of the process, the adsorbed quantity in
equilibrium with the liquid concentration is so high
that a very narrow saturation layer of the solid is
sucient for creating a high Hg ux towards the
particle (i.e. for removing a high quantity of mer-

Fig. 5. Eect of the external lm resistance.

Mercury removal from water

cury from the liquid phase). Therefore, in the low

diusivity region (the solid), the amplication of
mass ux due to the adsorption process implies that
a very little penetration layer is sucient for the
process to take place. In this case even a little external resistance becomes important. This behaviour,
evident at the very beginning of the process, could
not be observed during the experiments shown in
Fig. 2, since the change in the impeller speed took
place after 28 min.
Short discussion about the model
Results of Fig. 4 show that, in order to obtain a
reliable predictive model for ion exchange adsorption of heavy metals, a deeper analysis of transport
phenomena inside the particles has to be taken into
account.
At the same time, some observations have to be
done about the residual deviation between model
and experiment. This has to be mainly attributed to
the facts discussed as follows.
1. The equilibrium model does not consider the fact
that ion exchange is a chemical process and
neglects competition between H+ and Hg2+
ions. This assumption has been discussed in the
Experimental section of this paper, and is due to
the fact that we were mainly interested in verifying the eectiveness of a diusional model inside
particles to describe adsorption kinetics. Accordingly, kinetic measurements have been done only
at a single value of the initial pH 7; since no
eect of pH can be predicted with this simplied
model. This aspect will be the object of future
research, where a more detailed equilibrium
model will be considered.
2. As discussed, describing model simulation of
adsorption, characteristic times of the process are
very long (Table 2). This has important consequences also for equilibrium data. On the basis
of this result, the equilibrium data taken after
24 h could not be fully consistent. The evaluation
resulting from Eq. (14), is obtained with the hypothesis that the liquid phase can diuse through
the whole particle. However, no precise information is available about the geometrical properties of the resin, and liquid could diuse only in
a part of the whole solid volume. If so, this
would lead to lower characteristic times and to a
higher consistency of the equilibrium data.
3. Since the particle size distribution is wide, the
assumption of uniformity brings to an error in
the prediction of the kinetics, connected to the
uncertainty about the ``eective'' radius representing the whole mass of resin (and the time of
the process has a quadratic dependence to the
particle radius). Furthermore this ``eective''
radius probably varies with the initial concentration.
Finally, it seems useful to underline that the evalu-

2977

ation of the order of the time of diusion in Eq.

(14) conrms the fact that chemical kinetics is not
the limiting step.
Furthermore, from the results presented and
from the above considerations, the main geometrical properties of solid particles can be deduced. To
justify the change in adsorption rate with the initial
Hg concentration, solid particles must be characterised by diusion phenomena, and therefore by a
certain degree of porosity. On the other hand, since
the functional groups are added after the polymeric
matrix of the solid particles has been produced, the
whole volume of the solids is not necessarily active,
may be implying shorter characteristic times for the
adsorption process.
CONCLUSION

In this work a detailed experimental and theoretical analysis of mercury sorption on ion exchange
resins is presented. On the basis of the present
study, the following conclusions can be drawn:
. Sorption capacity of mercury on this resin is very
high, with the possibility to obtain extremely puried water.
. The degree of removal strongly dependent on the
initial pH of the solution: it decreases as the pH
increases. Furthermore pH decreases with time
during adsorption. This is due to the exchange
mechanism, by which protons are transferred
into the solution.
. Experiments show that the external lm resistance is not the limiting step; nevertheless its contribution cannot be neglected in the mathematical
model since, at the very beginning of the process,
the extremely high mass ux inside the particle
implies a non-negligible eect of external lm.
. The change in adsorption rate with the initial
mercury concentration implies that diusion
phenomena must take place inside particles.
. Despite the adopted equilibrium, description
neglects competition between H+ and Hg2+ ions,
the applied model is eective in the description of
the adsorption kinetics. However, further eort is
required to improve model consistency and performances and to describe the eect of pH.

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